CN106185948B - A kind of industrial silicon slag making dephosphorization process - Google Patents
A kind of industrial silicon slag making dephosphorization process Download PDFInfo
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- CN106185948B CN106185948B CN201610541809.4A CN201610541809A CN106185948B CN 106185948 B CN106185948 B CN 106185948B CN 201610541809 A CN201610541809 A CN 201610541809A CN 106185948 B CN106185948 B CN 106185948B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/037—Purification
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The invention discloses industrial silicon slag making dephosphorization process open in a kind of atmosphere, pickling processes including silicon after the slag making processing of calcium system and slag making, it is that blocky silicon material is fitted into medium frequency induction melting furnace, slag former melting is added after silicon fusing under high temperature, then silicon slag separation first preliminary removal part P is carried out, again the silico briquette after slag making is impregnated to form powder by dilute chloroazotic acid, then soaking and stirring removes remaining most P in hydrofluoric acid, by the silicon of the two step process, 95% or more impurity P removal, and simple process is mild.
Description
Technical field
The present invention relates to silicon purification techniques, more particularly to a kind of industrial silicon slag making dephosphorization process.
Background technique
Photovoltaic power generation has many advantages, such as cleaning, environmental protection, safety, resourceful, the effective alleviating energy crisis of energy and environment
The problems such as pollution, 21 century of being known as most potential new energy.Solar energy level silicon (SOG- needed for photovoltaic power generation at present
Si) mainly with the chemical technologies production of improvement Siemens etc., although purity is higher, theres are its, and at high cost, byproduct recycled, can
The problems such as environment can be polluted.Physical Metallurgy method be a kind of current most potential method for developing low-cost solar battery it
One, its main feature is that at low cost, purity meets the purity requirement of solar level silicon materials in 6N or more.
Because segregation coefficient of phosphorus (P) element in silicon is larger (0.35), individual pickling and directional solidification cannot all be removed
P in industrial silicon.At present except P technique is mainly vacuum intermediate-frequency melting and vacuum electron beam melting, but use vacuum intermediate-frequency molten
Refining and vacuum electron beam melting will will increase energy consumption, and be unable to continuous production.The Hiroaki of Tokyo Univ Japan
Kawamura et al. has delivered paper " REDUCTIVE on " The Minerals, Metals&Materials Society "
REMOVAL OF PHOSPHORUS IN SILICON USING CaO–CaF2SLAG".The paper utilizes pickling after first slag making
Method studies the polysilicon of p-doped.Use the CaO-CaF of mass fraction containing CaO 17.5%2Slag former, it is molten in vacuum
Pickling again after slag making 18 hours, highest can remove 90% or more phosphorus in furnace.But this method slag making overlong time, then
In addition vacuum condition, is difficult commercialization.Therefore developing a kind of low cost simple removal P method of purification has very big commercial promise.
Summary of the invention
The present invention provides a kind of industrial silicon slag making dephosphorization process, and which overcome existing deficiencies in the technology.
The technical solution adopted by the present invention to solve the technical problems is:
A kind of industrial silicon slag making dephosphorization process the following steps are included:
1) slag making: the silicon material by granularity in 1~100mm is fitted into medium frequency induction melting furnace, adjust the temperature to 1500 DEG C~
2000 DEG C, CaO-SiO is added after silicon fusing2-CaF2It is slag former to whole fusings, is poured after constant temperature melting 3min~5h cold
But to realize that silicon slag separates；The slag silicon ratio of the slag making is 0.2~3, and basicity is greater than 1；
2) pickling: by the silico briquette after slag making it is broken after be soaked in by the diluted chloroazotic acid of 2-10 times of volume ratio, under room temperature
2~30h of reaction takes out silicon powder and is rinsed with deionized water, be then soaked in mass fraction to form the silicon powder that granularity is less than 1mm
It for 0.5~10h in 1%~40% hydrofluoric acid and stirs, is then rinsed with deionized water, adding ammonium hydroxide precipitates silicon powder,
It takes out dry after silicon powder is rinsed with deionized water.
Preferably, in step 1), the temperature is 1500 DEG C~2000 DEG C.
Preferably, in step 1), the smelting time is 3min~5h.
Preferably, in step 1), the slag silicon ratio is 0.5-3.
Preferably, in step 1), the slag silicon of fusing is disposably poured out or silicon slag separately pours into below melting kettle
It accepts on graphite crucible, it is cooling, it is to be processed to take out silicon material.
Preferably, in step 2), the silico briquette impregnates 2~30h in chloroazotic acid.
Compared to the prior art, the invention has the following advantages:
1. silicon powder by slag making, reacts phosphorus with slag former and generates Ca by the present invention3P2Equal compounds, a part enter slag
In body, due to slag body is different with silicon liquid density and silicon slag separation to be removed, another part is then present in CaSi2Alloy
In, it is mixed with silicon, by subsequent acid cleaning process, removes silicon grain boundaries CaSi2Alloy, to realize the removal of P, removal rate is reachable
95% or more, removal effect is good, while can also remove metal impurities and B element, realizes the purification of industrial silicon.
2. slagging process can carry out under atmospheric conditions, without vacuumizing, process conditions are simple, answer suitable for actual production
With.
3. carrying out being broken into be put into the size of container and be soaked in chloroazotic acid by silico briquette when pickling forming powder, it is not necessarily to
Milling saves equipment and manpower.
4. acid cleaning process is without heating, reaction condition is mild, at low cost, is suitable for production application.
Invention is further described in detail for following embodiment；But a kind of industrial silicon slag making dephosphorization process of the invention is not
It is confined to embodiment.
Specific embodiment
A kind of industrial silicon slag making dephosphorization process includes slag making and pickling, is that powder silicon material is packed into medium frequency induction melting furnace
In, slag former melting is added after silicon fusing under high temperature, then carries out silicon slag separation first preliminary removal part P, then will be after slag making
Silico briquette impregnate to form powder by dilute chloroazotic acid, then soaking and stirring removes remaining most P in hydrofluoric acid, to realize
The efficient removal of P.
Embodiment 1
One, slag making is handled
Silicon raw material is metallurgical grade silicon, and purity is 98%~99%, and P content is in 5~200ppmv or so.By bulk silicon raw material
It is crushed to the bulk of 1-100mm size, is placed in oven and dried, is cooled to room temperature after being cleaned using deionized water.By graphite earthenware
Crucible is fitted into intermediate frequency furnace, accomplishes fluently furnace lining, cleans up graphite crucible inner wall.Above-mentioned blocky silicon material 140g is weighed, it is molten to be put into graphite
It refines in crucible, opens intermediate frequency power supply, elevate the temperature to 1500 DEG C.After silico briquette all fusing, then it will prepare and mixed
308g CaO2-SiO2-CaF2Slag former is uniformly added in melting kettle in batches, can specifically be divided into 3~10 times, often
Minor tick 30s~5min.After waiting slag former all to melt, constant temperature melting half an hour.Since silicon liquid is different with slag liquid density
And separate, silicon liquid and slag liquid are poured into the graphite cleaned up respectively and accepted in crucible, cooled to room temperature.After silicon liquid is cooling
Up to the silico briquette after slag making.Slagging process is operated in atmosphere without using vacuum equipment.
Two, pickling processes
Silico briquette after slag making is crushed to the silico briquette of the suitable size for the beaker that can put in, 2-10 times of volume ratio is dilute with pressing
The chloroazotic acid released impregnates, and impregnates 20 hours in glass beaker, takes out silicon powder, and rinsed silicon powder 5 times with deionized water；Again by silicon powder
It is rinsed silicon powder 3 times with hydrofluoric acid dips 1 hour of 10%, and with deionized water；Being eventually adding suitable ammonium hydroxide precipitates silicon powder,
It is rinsed silicon powder 4 times after silicon powder precipitating, then with deionized water, it is dry in baking oven.
Silicon after above-mentioned processing is subjected to elemental analysis with ICP-AES, the content of phosphorus and boron is as shown in table 1
1 ICP-AES test result of table (unit: ppmw)
| Element | Industrial silicon raw material | Slag making | Removal rate | Pickling after slag making | Removal rate |
| Phosphorus | 10.11 | 0.42 | 95.8% | <0.1 | > 99% |
| Boron | 5.66 | 1.66 | 70.7% | 0.95 | 83.2% |
Embodiment two
One, slag making is handled
Silicon raw material is metallurgical grade silicon, and purity is 98%~99%, and P content is in 5~200ppmv or so.By bulk silicon raw material
It is crushed to the bulk of 1-100mm size, is placed in oven and dried, is cooled to room temperature after being cleaned using deionized water.By graphite earthenware
Crucible is fitted into intermediate frequency furnace, accomplishes fluently furnace lining, cleans up graphite crucible inner wall.Above-mentioned blocky silicon material 140g is weighed, it is molten to be put into graphite
It refines in crucible, opens intermediate frequency power supply, elevate the temperature to 1800 DEG C.After silico briquette all fusing, then it will prepare and mixed
100g CaO2-SiO2-CaF2Slag former is added at one time in melting kettle.After waiting slag former all to melt, constant temperature
Melting 2 hours.Mixed liquor is disposably poured out, it is to be processed to take out silicon material after cooling.
Two, pickling processes
Silico briquette after slag making is crushed to the silico briquette of the suitable size for the beaker that can put in, 2-10 times of volume ratio is dilute with pressing
The dilute chloroazotic acid released impregnates, and impregnates 12 hours in glass beaker, takes out silicon powder, and rinsed silicon powder 5 times with deionized water；Again by silicon
Powder rinses silicon powder 3 times with hydrofluoric acid dips 2 hours of 30%, and with deionized water；Being eventually adding suitable ammonium hydroxide keeps silicon powder heavy
It forms sediment, is rinsed silicon powder 5 times after silicon powder precipitating, then with deionized water, it is dry in baking oven.
Silicon after above-mentioned processing is subjected to elemental analysis with ICP-AES, the content of phosphorus and boron is as shown in table 2
2 ICP-AES test result of table (unit: ppmw)
| Element | Industrial silicon raw material | Slag making pickling | Removal rate |
| Phosphorus | 80.62 | 1.19 | 98.5% |
| Boron | 19.94 | 2.48 | 87.6% |
Above-described embodiment is only used to further illustrate a kind of industrial silicon slag making dephosphorization process of the invention, but the present invention is not
It is confined to embodiment, according to the technical essence of the invention any simple modification to the above embodiments, equivalent variations
With modification, fall within the scope of protection of technical solution of the present invention.
Claims (4)
1. a kind of industrial silicon slag making dephosphorization process, it is characterised in that the following steps are included:
1) slag making: the silicon material by granularity in 1 ~ 100 mm is fitted into medium frequency induction melting furnace, adjusts the temperature to 1500 DEG C ~ 2000
DEG C, CaO-SiO is added after silicon fusing2-CaF2It is slag former to whole fusings, is poured cooling after constant temperature melting 3 min ~ 5 h
To realize that silicon slag separates；The slag silicon ratio of the slag making is 0.2 ~ 3, and basicity is greater than 1；
2) it pickling: is soaked in after the silico briquette after slag making is crushed by the diluted chloroazotic acid of 2-10 times of volume ratio, reacts 2 under room temperature
~ 30 h pour out wang aqueous solution and rinse silicon powder with deionized water, be then soaked in quality to form the silicon powder that granularity is less than 1mm
Score is 0.5 ~ 10 h in 1% ~ 40% hydrofluoric acid and stirs, and is then rinsed with deionized water, and adding ammonium hydroxide precipitates silicon powder,
Pour out after ammonia spirit rinsed with deionized water it is dry after silicon powder.
2. industrial silicon slag making dephosphorization process according to claim 1, it is characterised in that: in step 1), the temperature is
1500℃~1800℃。
3. industrial silicon slag making dephosphorization process according to claim 1, it is characterised in that: in step 1), the slag silicon ratio is
0.5~3。
4. industrial silicon slag making dephosphorization process according to claim 1, it is characterised in that: be the slag that will be melted in step 1)
Silicon is disposably poured out or silicon slag is separately poured into and accepted on graphite crucible, cooling, and it is to be processed to take out silicon material.
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| CN106744977A (en) * | 2016-12-09 | 2017-05-31 | 永平县泰达废渣开发利用有限公司 | A kind of graphite furnace lifting method of the molten silicon of utilization induction furnace |
| CN107055545B (en) * | 2016-12-09 | 2019-01-25 | 成都斯力康科技股份有限公司 | A kind of technique carrying out melting production silicon ingot using silicon powder |
| CN107055547A (en) * | 2017-04-13 | 2017-08-18 | 苏州振吴电炉有限公司 | The preparation technology of HIGH-PURITY SILICON slag former |
| CN108862279A (en) * | 2018-05-30 | 2018-11-23 | 江苏佳宇资源利用股份有限公司 | A kind of metallic silicon formula and preparation method thereof |
| CN109052409A (en) * | 2018-10-19 | 2018-12-21 | 东北大学 | A kind of high scrap silicon preparation HIGH-PURITY SILICON/silicon alloy method of induction melting |
| CN113860314A (en) * | 2021-09-29 | 2021-12-31 | 新疆大全绿创环保科技有限公司 | Method for producing industrial silicon by using silicon-containing solid waste |
| CN115465865B (en) * | 2022-08-11 | 2023-08-04 | 商南中剑实业有限责任公司 | Device and method for synchronously removing boron impurities and phosphorus impurities in industrial silicon |
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| JPH04193706A (en) * | 1990-11-28 | 1992-07-13 | Kawasaki Steel Corp | Refining method for silicon |
| CN101844768A (en) * | 2010-05-20 | 2010-09-29 | 厦门大学 | Method for removing phosphorus and boron from metallurgical-grade silicon |
| CN104291340A (en) * | 2013-10-15 | 2015-01-21 | 中兴能源（唐山）节能有限公司 | Method for removing phosphorus in industrial silicon |
| CN104556051A (en) * | 2014-12-25 | 2015-04-29 | 大连理工大学 | Method for removing boron element in polysilicon slag former with metallurgy method and prepared regenerated slag former |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04193706A (en) * | 1990-11-28 | 1992-07-13 | Kawasaki Steel Corp | Refining method for silicon |
| CN101844768A (en) * | 2010-05-20 | 2010-09-29 | 厦门大学 | Method for removing phosphorus and boron from metallurgical-grade silicon |
| CN104291340A (en) * | 2013-10-15 | 2015-01-21 | 中兴能源（唐山）节能有限公司 | Method for removing phosphorus in industrial silicon |
| CN104556051A (en) * | 2014-12-25 | 2015-04-29 | 大连理工大学 | Method for removing boron element in polysilicon slag former with metallurgy method and prepared regenerated slag former |
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